Copperable polyazo dyestuffs



United States Patent ce COPPERABLE POLYAZO DYESTUFFS Hans-Rudolf Byland, Riehen, Switzerland, assignor, by mesne assignments, to Saul & Co., Newark, N. J., as

, nominee of Fidelity Union Trust Company, executive trustee under Sandoz Trust No Drawing. Application May 28, 1956 Serial No. 587,484

Claims priority, application Switzerland June 3, 1955 6 Claims. (Cl. 260-172) The present invention relates to copperable polyazo dyestuffs.

The copperable polyazo dyestuffs of the present invention may be represented by the formula wherein R maybe hydrogen, substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl, z may be hydroxy or carboxy,

aminoazo compound of the formula HO S wherein R has. thepreviously-recited significance, and z may be -OH or -COOH, and nucleus A may con- 2,835,662 Patented May 19 58 tain further substituents, and with one mol of a compound containing an enolizable keto group and'capable of coupling in a position vicinal to the latter.

Illustrative'of compounds which contain an enolizable keto group and are capable of coupling in a position vicinal to the latter are for example:

5-pyrazolones Acylacetic acid amides Acylacetic acid arylamides Acylacetic acid alkylamides Malonic acid derivatives Barbituric acid derivatives Acetylacetone Benzoylacetone 4-hydroxy-1-alkylquinolines, and Dihydroxyquinoline Especially useful 5-pyrazolones comprise:

3-methyl-5-pyrazolone l-phenyl-3-methyl-5-pyrazolone l-phenyl3-methyl-5-pyrazolone-3-sulf0nic acid amide 1-phenyl-3-metl1yl-5-pyrazolone-4-sulfonic acid amide 1- (3 '-methylsulonyl) -phenyl-3 -methyl-5-pyrazolone 1-(4-methylsu1fonyl)-phenyl-3-methyl-5-pyrazolone 1-( 3 -nitro) -phenyl-3-methyl-5-pyrazolone 1-(4'-nitro)-phenyl-3-methy1-5-pyrazolone' 1- 3 '-chloro) -phenyl-3 -methyl-5-pyrazolone l-(4-chloro)-phenyl-3-methyl-5-pyrazolone 1-(2, -dichloro)-phenyl-3-methyl-5-pyrazolone, etc.

Even more important are the acylacetic acid arylamides and alkylamides, and particularly acetoacetylaminobenzene and its derivatives nuclearly substituted by halogen atoms, amino, nitro, alkylsulfonyl, sulfonic acid, sulfonic acid amide, carboxylic acid and/or azo groups;

' also 1 acetoacetylaminonaphthalenes, 2 acetoacetyl- "aminonaphthalenes,

1 acetoacetylaminonaphthalene- "monosulfonic acids, 1-acetoacetylaminonaphthalene diin any desired order of succession with one mol of an 71 sulfonic acids, 2- acetoacetylaminonaphthalenemonosulfonic acids and 2-acetoacetylaminonaphthalenedisulfonic I acids, all of which may be further substituted.

Illustrative of suitable acylacetic acid alkyl amides are l-acetoacetylaminohexane l-acetoacetylaminooctane 1-acetoacetylamino-Z-ethylhexane l-acetoacetylamino-2,2-dimethylethane, etc.

' 1,l'-diphenyl of Formula II with the aminoazo compound of Formula III is preferably carried out in a sodaalkaline medium. The resultant intermediate is either isolated or else used in solution, without special working up, and coupled with the azo component which contains an enolizable keto group and is capable of coupling in a position adjacent to such group. In order to accelerate the second coupling, it is advantageous to add to .the reaction solution an organic tertiary base, such for example as pyridine, quinoline or a technical pyridine base mixture. The coupling of the tctrazo compound with the two azo components may also be carried out in the reverse order. The resultant polyazo dyestufis are, if necessary, salted out of the reaction solution, filtered 01f and dried.

The s o-obtai n ed polyazo dyestuffs dye cotton and of 0.8 part of the trisazo dyestufi of the formula set forth fibers of regenerated cellulose in violet-red shades which in the preceding paragraph is then added and the bath is are displaced toward gray to deep black by aftertreatheated to boiling within a period of 30 minutes. During ment with copper-yielding agents. The coppencontainthe heating, 3 parts of sodium sulfate are added to the lug dyeings are distinguished by outstanding fastness to bath portionwise in theform of a concentrated aqueous light, to washing and to perspiration and by very good solution. The bath is keptat the boil for 30 more minutes, discharge-ability. By suitably selecting the water-solu- 1 part of sodium sulfate is then added, after which the bilizing groups, dyestuffs with a high water-solubility are bath is allowed to cool slowly to 40. The dyed material obtained. This property enables the dyestuffs to be is then thoroughly washed, and then treated for 30 minutes brought onto the fiber by modern continuous dyeing at 70 in a fresh bath consisting of 300 parts of water, methods. A further outstanding property of the new 0.3 part of acetic acid and 0.3 part of copper sulfate. The

dyestuffs is that they reserve acetate silk. resultant metallized dyeing is rinsed and dried.

The following examples set forth, by way of illustra- Instead of copper sulfate in the aftertreating bath, use tion, representative embodiments of the invention; In may also be made of a polyalkylenepolyamine which these examples, the parts and percentages are by weight; contains copper in complex combination. the temperatures are in degrees centigrade. EXAMPLE 2 EXAMPLE 1 27.2 parts of 4,4'-diamino-1,1'-diphenyl-3,3-dicar- 27.2 parts of 4,4-diarnino-1 ,1'-diphenyl-3,3'-dicarboxylic acid are tetrazotized. Then a neutral aqueous boxylic acid are tetrazotized. To the obtained tetrazo solution of 3.0.7 parts of 2-acetoacetylaminonaphthalenesolution, ice-cold, there is added a solution of 51;.4 parts 6-sulfonic acid is run into the obtained tetrazo solution. of the aminoazo compound obtainable by acid coupling 40 parts of sodium bicarbonate are then added portionof diazotized 2-amino-1-hydroxybenzene-4-sulfonic acid wise to the mixture. Upon completion of the formation amide with 2-phenylamino-S-hydroxynaphthalene-7-su1- of the diazomonoazo intermediate, there is added to the fonic acid, 10 parts of sodium carbonate and 900 parts reaction mass a solution of 48 parts of the aminoazo of Water. Thereupon a concentrated aqueous solution of compound obtained by the acid coupling of diazotized parts. of sodium carbonate are forthwith run into the 2-amin0-1-hydroxy-4-nitrobenzene with 2-phenylaminocoupling. mixture. The formation of the diazodisazo 5-hydroxynaphthalene-7-sulfonic acid, 125 parts of techintermediate is completed in a short time. There is then nical pyridine base mixture and 300 parts of water. The added to the solution of the latter, a solution of 17.7 parts 30 precipitated trisazo dyestuff is filtered off and dried. It of acetoacetylaminobenzene in 600 parts of water, the corresponds to the formula SOzH H NH 5 Bots NH OOH H mixture stirred for several hourswhile cooling with ice, and is a dark powder which dissolves in water to yield and the resultant trisazo dyestuff salted out by the addia red-violet colored solution and whose coppered dyeings tion of sodium chloride. The dyestuff is then filtered ofi on cotton and fibers of regenerated cellulose are of a black and dried. The new copperable trisazo dyestufi which shade which is fast to light, to washing and to perspiration. corresponds to the formula The following table sets forth additional examples in B PN a is a dark powder which dissolves in water to yield a tabular form, the procedure followed being according to violet-red eolored solution and which dyes cotton. and 7 the preceding examples. The so-obtained dyestuffs are fibers of regenerated cellulose by the single-bath or two built up from a 4,4'-diamino-1,1'-diphenyl of Formula II. bath coppering process in black shades'of outstanding To'characterize the dyestuffs, column 1 sets forth the fastness to light, to washing and to perspiration. aminoazo compound of Formula III, and column 2 sets 10 parts of prewetted cotton are introduced into 300 forth the second azo component. Column 3 indicates the parts ofwater at 40 A concentrated aqueoussolution shade of the coppered dyeings on cellulose fibers.

2,835,662 7 5 8 EXAMPLE 45 two-bath coppering processes in black shades of outstand- 27.z parts of 4,4-diamino -"1,"1' -diphenyl-'3,3'-dicaring fasmess 3 light Washing peopirafim boxylic acid are tetrazotized. To the obtained tetrazo For the mlxture of acetoacetylammobenzene and solution, ice-cold, there is added a solution of 51.4 parts PhenY1'3'mothyl's'pyrazolone which forms the second 310 of the aminoazo compound obtainable by acid coupling a Component, mixing Proportions difiel'ont from 111 y be of diazotized Z-amino-l-hydroxybenzene-4-sulfonic acid 01108611, 6 g-, 511 or 211 Altemativoly, The two amide with 2-phenylarnino-5-liydroXynaphthalcne-7-sulconstituents of the second azo component may be re- -fonic acid, 10 parts of sodium carbonate and 900 parts placed by their derivatives substituted by halogen atoms, of water. Thereupon a concentrated aqueous solution of 10 itm, methoxy, ethoxy, methyl-sulfonyl and/orsulfonic 30 parts of sodium carbonate are forthwith run into the acid amide groups.

coupling mixture. The formation of the diazodisazo intermediate is completed in a short time. There is then added to the solution of the latter. a solution of 8.9 parts of acetoacetylaminobenzene and 8.7 parts of l-phenyl- 1r 3-methyl-5-pyrazoione in 600 parts of water and 4 parts of sodium hydroxide. The mass, ice-cooled, is stirred for several hours and the two trisazo dyestulfs thus formed EXAMPLE 46 When the 8.9 parts of acetoacetylaminobenzene employed in Example 45 as a constituent of the second azo component are replaced by 16.5 parts of sodium 2-acetoare subsequently salted out by the addition of common acfitylaminonapilthalefie6611mmate, trisazo y fl salt, then filtered off and dried. They correspond to the 20 mlxt r is m the y e f whlch als sh w exformulae cellent fastness properties.

Bog-NH:

if N

| HOgS- NH- 5 h-on l coon H H: H00

and

SOs-NH! i CH1 15' g V H V N= O l \C= -N=N N=N H0O OOH H The trisazo dyestuff mixture is a dark-colored powder The formulae of the two trisazo dyestuffs which form which dyes fibers of regenerated cellulose by the oneor the mixture are SOaH Sol-NH! E NH nos H V l r to G a-N=N N= -02: 0011 H n, nooo and oa-N15 N=C v I H O I Hots NH .\C=CN=N r N=N By varying the mixing proportions of the two constituents of the azo component, dyestufis mixtures can be obtained whose coppered dyeings display a more greenish or more reddish shade than is the case when the mixing proportions given in the preceding paragraph are chosen.

In place on. the 2-acetoacetylaminonaphthalene-G-sul- H fonic acid used in the present instance, other 2- or l-acetoacetylaminonaphthalene monosulfonic acids as well as mixtures of such can be employed with equal success. It

is also possible to replace the 1-phenyl-3-methyl-5-pyraz- 10 olone by 1-phenyl-3-methyl-5-pyrazolones substituted in the phenyl nucleus by halogen atoms, nitro, methylsulfonyl and/ or sulfonic acid amide groups.

.1: wherein R is 'a' nimher'selected'ffdifi the gro" p consisting of hydrogen, lower alkyl, cyclohexyl, benzyl'-and'mono'- nuclear carbocyclic aryl, z is selected from the .group consisting of hydroxy and carboxy,

SOs-NH! O nms NH-O (J-N=N N=N (Ii-0H V on n hm H000 Formulae of representative dyestuffs set forth in the foregoing table are:

EXAMPLE 24 HOaS I 0 C-N= N=N (ILL-OH OOH H; H000 EXAMPLE 28 HNONH A} At H015 0 0 (11H; A,N=N N:

OOH H H: H0O

EXAMPLE 37 to s ()H L 1H, H00 I Having thus disclosed the invention what is claimed is:

1. Copperable polyazo dyestutfs which correspond to 65 the formula I NO 3. The copperable trisazo dyestufi which corresponds 'to the formula (Ii-NL-N A. M -on 4. The copperable trisazo dyestufi which corresponds to the formula g QQ a soon He HOOC 5. The copperable trisazo dyestufi which corresponds to the formula 6. The copperable trisazo dyestuff which corresponds to the formula soin N 5H NH O HOzS NIH-O 0-011 1 L OOH H References Cited in the file of this patent UNITED STATES PATENTS 

1. COPPERABLE POLYAZO DYESTUFF WHICH CORRESPOND TO THE FORMULA 